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It is universally acknowledged that ligands can improve the reaction activity to simplify the reaction operating conditions and enrich the applicability of the reaction. Therefore, we developed -octylglycine ligand-accelerated Pd-catalyzed -arylation of benzoic acids under mild conditions with just 6 h; moreover, this -octylglycine ligand was successfully implemented to carboxyl-directed Pd-catalyzed β-C(sp)-H arylation and arylation of phenylacetic acids under mild conditions.
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http://dx.doi.org/10.1021/acs.joc.4c00643 | DOI Listing |
J Am Chem Soc
June 2025
Department of Chemistry, The Scripps Research Institute, La Jolla, California 92037, United States.
Selective fluorination of C()-H bonds is a highly valuable transformation in organic synthesis and drug discovery. However, achieving methylene C-H fluorination of native substrates remains a significant challenge, as it typically requires external directing groups to facilitate catalyst-substrate binding. Herein, we report a ligand-accelerated Pd-catalyzed methylene β-C-H fluorination of native amides using a bidentate neutral amide-pyridone ligand.
View Article and Find Full Text PDFOrg Lett
May 2025
School of Pharmacy, Shanghai University of Medicine & Health Sciences, Shanghai 201318, China.
Pd-catalyzed cascade annulation of 2-iodoanilines with ,3-diphenylpropiolamides was achieved, which afforded a series of indolo[2,3-]quinolinones with good yields and functional group compatibility. Previously, the retro-synthetic routine for the indolo[2,3-]quinolinone skeleton has often involved intramolecular disconnection of the C(sp)-C(sp) bond at variable positions, which necessitates the construction of an indole or quinoline reactant with multiple pre-set functionalities. Meanwhile, using the C-H activation strategy to construct indoloquinoline is limited to cases in which the reactant must be an indole bearing a nonremovable directing group.
View Article and Find Full Text PDFJ Org Chem
June 2024
State Key Laboratory of Materials-Oriented Chemical Engineering, School of Pharmaceutical Sciences, Nanjing Tech University, Nanjing 210009, China.
It is universally acknowledged that ligands can improve the reaction activity to simplify the reaction operating conditions and enrich the applicability of the reaction. Therefore, we developed -octylglycine ligand-accelerated Pd-catalyzed -arylation of benzoic acids under mild conditions with just 6 h; moreover, this -octylglycine ligand was successfully implemented to carboxyl-directed Pd-catalyzed β-C(sp)-H arylation and arylation of phenylacetic acids under mild conditions.
View Article and Find Full Text PDFNat Commun
November 2023
The Scripps Research Institute (TSRI), 10550 North Torrey Pines Road, La Jolla, CA, 92037, USA.
A wide range of Cu(II)-catalyzed C-H activation reactions have been realized since 2006, however, whether a C-H metalation mechanism similar to Pd(II)-catalyzed C-H activation reaction is operating remains an open question. To address this question and ultimately develop ligand accelerated Cu(II)-catalyzed C-H activation reactions, realizing the enantioselective version and investigating the mechanism is critically important. With a modified chiral BINOL ligand, we report the first example of Cu-mediated enantioselective C-H activation reaction for the construction of planar chiral ferrocenes with high yields and stereoinduction.
View Article and Find Full Text PDFOrg Lett
October 2022
Department of Chemistry, The Scripps Research Institute, 10550 N. Torrey Pines Road, La Jolla, California 92037, United States.
Here, we report the development of a class of bifunctional monoprotected amino-imidazoline (MPAI) ligands and their applications in Pd-catalyzed C()-H arylation of free aliphatic acids. The newly developed MPAI ligand allows the use of 1.0 equiv of aliphatic acids containing an alpha hydrogen for the first time.
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